DE2302400A1 - POLYURETHANE INTERLAYER FOR LAMINATED SAFETY GLASS - Google Patents

Description

DR. BERG DirL, -ING. STAPF

PATENTANWÄLTE 8 MÜNCHEN 86, POSTFACH 860245 2302400

Dr. Berg Dipl.-Ing. Stapf, 8 Munich 86, P. O. Box 86 0245

Lawyer file number 23 360

Your reference Our reference 8 MÖNCHEN 80 ] J ₁ Jctfl. 1973

Your ref. Our ref. 23 360 MauerkircherstraBe 45

Monsanto Company St. Louis / USA

Polyurethane intermediate layer for laminated safety glass.

The present invention relates to laminated glass articles and, more particularly, to laminated glass comprising using a polyurethane intermediate layer became.

Laminated glass bodies enjoy widespread use in vehicles and structural applications .

Laminated safety glass used as a windshield of vehicles has several severe requirements Requirements meet the minimum security requirements to suffice. These requirements are a

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high level of clarity or freedom from haze to allow maximum light transmission through the laminate to ensure. This is necessary to ensure that the person driving the vehicle is aware of the below has the maximum possible visibility under the respective circumstances. The intermediate layer should also be a Have sufficient adhesion to the glass to prevent broken glass from getting inside the vehicle flying around in the event that an object hits the laminate and breaks the glass. Another requirement of the laminate is that it have sufficient impact strength to withstand the To restrain passengers of the vehicle within the vehicle in the event of an impact. Further in this regard, the laminate should have the ability to absorb the impact in the event that a passenger of the vehicle is thrown against the laminate. In addition to the safety requirements mentioned above, which are of the utmost importance, the laminate should have sufficient edge stability that the Prevents water from penetrating the edges of the laminate, which would cause discoloration or de-amination and so reduce the life of the laminate.

The polyurethane interlayers for laminated safety ^{glass described in U.S. Patents 2 m f> 1 f} ), 2,864,780, 3,226,354 and 3,388,032,

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have more than one disadvantage, making them generally suitable for use as an intermediate layer unsuitable in laminated windshields. For example, from aromatic diisocyanates, such as toluene diisocyanate or 4,4'-methylenebis (phenyl isocyanate) manufactured interlayers tend to discolour, which leads to their use as automobile windshields impaired. On the other hand, the use of aliphatic diisocyanates, such as hexamethylene diisocyanate, with a polyester such as polybutylene adipate by clouding and / or by the Lack of impact resistance characterized thereby these materials become unacceptable as an intermediate layer in automobile windshields. The so-called pour-in-place polyurethane interlayers, cast in place, which are described in Canadian patents 673,674 and 673678 pose additional problems as a result that the strength of the pour-in-place film difficult to control is. The epoxy resin used, which is used to react with the polyurethane, tends to be used to bring in a pre-staining. In many cases the impact strength of the previous intermediate layers fluctuates considerably. Many of the well-known polyurethane interlayers Child therefore unsuitable: because of low impact strength of the laminates obtained and this W.nnon not, recommended for windshields'

Ο η 3 ^u:; , η / 11 η b

not even if there is color, haze and edge stability pose no problems. The above problems with the previous polyurethane interlayers connected are solved by the polyurethane interlayers of the present invention been. Laminated glass bodies made from polyurethane interlayers from the invention, show excellent impact strength over a wide temperature range, freedom from discoloration, excellent clarity and excellent edge stability. · The laminated safety glass, which is made up of the polyurethane interlayers of the present invention is particularly suitable for use as windshields suitable in vehicles of all kinds. The polyurethane interlayers of the present invention are made from 1. a diisocyanate, which is an isomeric mixture of 4,4'-methylenebis (cyclo'-hexyl isocyanate) (hereinafter referred to as MBI), 2. a polyester with a melting point above 42 ° C, which is a condensation reaction product of a dicarboxylic acid and a diol compound, and 3. one Chain extender, which is an οΙ, αλ diol with 2 - 16 carbon atoms is.

The solid phase of the glass body can be any solid transparent material such as glass, polystyrene, polyvinyl chloride , Polycarbonate, polymethyl methacrylate, etc. The preferred material for automotive glass bodies

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is glass.

The MBI used in the present invention is an isomeric mixture having a trans-trans content of 0-30% by weight, a cis-cis content of 0-25% by weight and a cis-trans content of 45-90% by weight, wherein the total amount of isomers is 100% by weight. The preferred mixture of isomers has a trans-trans content of 15-25% by weight, a cis-cis content of 10-20% by weight and a cis-trans content of 55-75% by weight. The most preferred isomer mixture has a trans-trans content of 18-22% by weight, a cis-cis content of 12-18% by weight and a cis-trans content of 60-70% by weight.

The polyester component, which is mixed with the isomer mixture of the MBI is implemented is a condensation reaction product of a dicarboxylic acid with 2 to IO carbon atoms and one Diol compound with 2-16 carbon atoms.

Examples of suitable dicarboxylic acids used to make the polyester are straight chain aliphatic acids such as oxalic, halonic, amber, glutaric, adipic, pimeline and subarin, azelaic and Sebacic acid. The use of branched aliphatic dicarboxylic acids, such as alkylglutaric or adipic acid, is contemplated being the alkyl group. Contains 1-6 carbon atoms, such as 2-methylglutar, 2,4,4-trimethyladipic and 3-ethyladipic acid, of dicarboxylic acids, the heteroatoms in the main or side

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chain, such as oxydiacetic acid, thiodiacetic acid, 2-dialkylaminoadipic acid, 3-methoxyglutaric acid, from alicyclic dicarboxylic acids such as cyclohexane, cyclopentane and the corresponding alkyl-substituted dicarboxylic acids and heterocyclic dicarboxylic acids, such as tetrahydrofuran, Tetrahydrothiophene, tetrahydropyranedicarboxylic acid, etc.

Those preferably used in the present invention Dicarboxylic acids are the straight-chain aliphatic dicarboxylic acids and especially glutaric, adipic and Azelaic acid.

Examples of diol compounds which are reacted with the dicarboxylic acid to form the polyester are linear aliphatic oil, copper dials with 2 - 10 carbon atoms, such as ethylene glycol, 1 _f 3-precpane glycol, 1,4-butane glycol, 1,5 - Pentane glycol, 1,6-hexane glycol, 1,7-heptane glycol, 1,8-octanediol, 1,10-docanediol, etc. The use of branched aliphatic glycols such as 1,2-propanediol, 2, 3-butanediol, 2,2-dintethylpropanediol, 3-methyl ~ 1,5-pentanediol, phenyl-1,2-ethanediol, 2,4,4-trimethylhexanediol, 3-methoxypentanediol, of alicyclic diols, * i? Ie cyclohexanediols, Cyclopentanediols, cyclohexanedimethanols, decahydronaphthalenediols, 2,2-bis- (4-hydi-OKvcyclohexyl) propane? of heterocyclic glycols, such as tetrahydrofuran diols, N-hydroxyethyl-4-propaiiolpiperidine, 1,2-bis [jN- (2-hydroxyethyl) -4-piperidyl ethane, and of other glycols,

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such as ethoxylated or propoxylated dihydroxy compounds, such as bisphenol A, hydrogenated bisphenol A and cyclohexanediol.

The glycols preferably used in the present invention are aliphatic dj-, UJ-diols and especially ethylene glycol, 1,4-butane glycol and 2,2-dimethylpropanediol.

The polyester is made by any of those methods which are already known. The at the Polyesters used in the present invention are those having a melting point above 42 ° C and preferably above 45 ° C. The polyester preferably has an average molecular weight of 500-4000 and more preferably from 800-1200. The reaction of the aliphatic dicarboxylic acid and the aliphatic dihydro compound should be carried out in such a way that terminal hydroxyl groups are created on the polyester will. In addition, when choosing the dicarboxylic acid and glycol components that are used to manufacture of the polyester, care should be taken to ensure that a resulting polyester is made with a molecular weight of 500-4000 and a melting point above 42 ° C is created. One such Selection processes are already well known to the person skilled in the art.

The third component that is used to make the polyurethane interlayers of the present invention

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is used is a chain extender that is an OL, IV diol with 2-16 C atoms. Examples of these diols are straight-chain aliphatic oi, W diols with 2 to 6 carbon atoms, such as 1,2-ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol . The use of branched aliphatic glycols, such as 1,2-propanediol, 2,3-butanediol, 2,2-dimethylpropanediol, 3-methyl-1,5-pentanediol, phenyl-1,2-ethanediol, 2,4, 4-trimethylhexanediol, 3-methoxypentanediol, etc., of-alicyclic diols, such as cyclohexanediols, cyclopentanediols, cyclohexanedimethanols, decahydronaphthalenediols, 2,2-bis {4-hydroxycyclohexy1) propane, etc., and of diols, such as the ethoxylated or propoxylated diols, such as the ethoxylated or propoxylated compounds. for example bisphenol A, hydrogenated bisphenol A, cyclohexanediol, etc. are contemplated. Small amounts of water can be used in combination with the above chain extenders. The use of the corresponding thiols is also contemplated. The preferred chain extenders are the straight-chain aliphatic oC '/ Ujf diols and in particular 1,3-propanediol, 1,4-butanediol and 1,5-pentanediol. Particularly preferred for use in the present invention are 1,3-propanediol and 1,5-pentanediol because of the excellent edge stability and clarity they impart to the laminates. The polyurethane interlayers are made by implementation

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of the Di i socyanatpolye ster s and of the cC- (jLHDiolkettenyerlängerers obtained according to known conventional methods. The particular methods used in the working examples of the present invention are explained in more detail below.

In the working examples given below, the polyurethane materials of the present invention are used expediently by a 1-step or 2-step process manufactured.

In the 1-step method of the DJ, U) -Diolkettenverlängerer and the degassed polyester is introduced into a dry four-necked flask provided feinlaß with a mechanical stirrer, thermometer and dry Stickstof, and at 20 - 50 ⁰ C cooled.

The diisocyanate is added, the mixture is degassed and then ^{cooled to about 40 °} C. as long as no crystallization takes place. The catalyst is then added and stirred for one minute until degassing begins again. Degassing is continued for 4 minutes if possible. After degassing, if possible, continue stirring for a further 2 minutes. If at any point during this procedure the temperature reaches 70 ° C or the rate of temperature rise is 10 ° C / min. exceeds, the reaction mixture is immediately poured into a mold. The reaction conditions of 80-100 ° C for times of

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2-144 hours are used to cure the polymer.

The 2-step process includes

a) prepolymer production and

b) polymer production.

During prepolymer production, the diisocyanate is introduced into a dried four-necked flask, which fitted with a mechanical stirrer, thermometer, dropping funnel and dry nitrogen inlet. The polyester that has been degassed and made of The volatiles have been stripped up to 95 ° C and 0.5 mm Hg, is added through a dropping funnel fed.

The reaction temperature is increased to 80-85 ° C. by heating, cooling and / or adjusting the rate of addition of the polyester held. Heating is continued for 5 hours. Then each has exotherm Heat development stopped. During the last half hour the prepolymer is degassed at 1-5 mm Hg.

Immediately after the prepolymer prepared as above has been degassed, a sample is taken and the percentages Isocyanate (and consequently its equivalent weight) is determined according to ASTM regulation D 1638-61T. The calculated amount of the cCj / CÜ diol chain extender is then added to the prepolymer kept at 45-50 ° C. This temperature is necessary to

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obtain the viscosity required for proper mixing. The reaction will last 30 minutes - during is degassed - stirred and then a calculated amount of catalyst is added and the degassing continued. The reaction is stirred as long as the temperature rise 10 ° C / min. does not exceed or the temperature does not exceed 70 ° C. Once the stirring and degassing was stopped, that became Immediately pour the reaction mixture into a mold. the Curing was carried out as described above. The equivalent ratio of diisocyanate / polyester / chain extender in the polyurethane interlayers of the present invention is in the range of 1.5 / 1.0 / 0.5 to 4 / 1.0 / 3. The more preferred equivalent ratio of diisocyanate / polyester / chain extender ranges from 2.0 / 1.0 / 0.94 to 2.3 / 1.0 / 1.23. The thickness of the intermediate layer made from the polyurethane prepared above can be by Control the depth of the shape can be adjusted. If necessary, a large polyurethane cake can be made and intermediate layers of suitable thickness can be obtained from the film by scraping. According to still other methods, the intermediate layer is made by a continuous casting process or by continuous conversion of the raw materials in an extruder to form a continuous sheet of material obtain. Other conventional film extrusion processes can also be used.

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The thickness of the polyurethane interlayers of the present invention can be over a wide range vary. The intermediate layer is preferably from 0.0051 cm to 304.8 cm thick.

The interlayers of the present invention are more preferably from 0.025 cm to 0.114 cm in thickness. Before the laminate was made, the intermediate layer was adjusted to the desired moisture content, usually to 0.05-1.0% by weight, conditioned. In the examples given below, sets of 10 glass laminates individually by placing a 0.076 cm intermediate layer between two 30.5 χ 30.5 χ 0.318 cm Glass plates made. These arrangements are then a temperature of about 135 ° C and one

Subjected to pressure of 13 kg / cm for approximately 10 minutes to prepare the laminated safety glass. These laminates are then subjected to an average height-to-break test similar to those recently established Subject to test specifications drawn up by the Society of Automotive Engineers, the subcommittee of auto glass.

Essentially, the average height of break test involves placing the laminate in a horizontal position a frame or edge holder and you let a 2.268 kg steel ball against a certain height fall about the middle of the laminate. This test is repeated with increasing ball drop heights in order to

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To determine the approximate height in meters at which 50% of the laminates tested will withstand penetration. With In other words, the mean breaking height of a laminate is a measure of the ability of the laminate to generate energy to adsorb an impact object. The laminates are checked for haze according to ASTM protocol D 1003-61 and tested for relative haze by comparative test laminates with a known standard under ultraviolet light.

The standard used is a common plasticized polyvinyl butyral glass laminate of the type shown in Automotive windshields being used. The standard interlayer used is 0.076 cm film of polyvinyl butyral plasticized with 42 parts per 100 parts of resin triethylene glycol di (2-ethyl butyrate). The resin is characterized by a hydroxyl group content of 19.5%, a residual acetate content of 1.9% and a butyral content of 79.5%. The glass used is a polished glass plate with a 0.318 cm thick. The standard gives a relative value of one (1). The numerical values listed below result from the ASTM test. The edge stability of the laminates is tested according to the test method ASA 5,3,2 with the exception that a 7.62 cm 12.7 cm laminate is used in place of the 30.5 χ 30.5 cm laminate specified in ASA 5.3.2 will, and the laminates will be at two (2) and four (4) week intervals instead of two week intervals

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which are specified in ASA 5,3 , 2 , checked. This test is described in "American Safety Code for Safety Glazing Materials for Glazing Motor Vehicles Operating on Land Highways" and has been published under No. Z26, 1-166 of the American Standards Association.

The following examples illustrate the invention. All parts and percentages are parts and percentages by weight, unless otherwise stated. Examples 1-5

The following examples illustrate the preferred embodiments of the present invention. In these examples, the diisocyanate used is an isomeric mixture of 4,4'-methylenebis (cyclohexylisocanate) with a trans-trans content of 15-25% by weight, a cis-cis content of 10-20% by weight and a Gis-trans content of 55-75% by weight. This material is commercially available under the name Hylene W (from duPont). The poly (l, 4-butylene adipate) melting at 49.0 to 50 ⁰ C. In the examples 1, 2 and 5, the 1,4-butanediol is used as chain extenders, while 1,3-propanediol as a chain extenders in Examples 3 and 4 is used. In Examples 1 to 4, the polymer is prepared in a one-step process using 0.0125% by weight of a dibutyltin diacetate catalyst.
Example 5, which is essentially the same as that

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of Example 2 is prepared by a 2 step process using 0.025% of a dibutyltin diacetate catalyst manufactured. The results of these examples are summarized in Table I below.

Table I.

Poly
ester
Molecu Summary of examples 1 Reaction
conditions Hours. - 5th I. 2.44 -18 ° C 21 ° C 49 ° ( Rela
tive
! Trü largew. JL til lip
° c 96 3.29 ■ exercise
- (4) at
game 1OO7 polymer
together
settlement 90 96 medium fracture
n (2) height of the lami
nates (meters) (3) 2.97 6.4 9.5 5.8 <l, 0 1O24 NCO: glycol:
KV (1) 90 96 3.32 > 12.8 11.0 4.3 0.83 1OO7 2.2: 1.0: 1.14 90 96 3.24 7.6 8.2 4.0 <l, 0 1 1024 2: l? O, 94 90 96 9.1 7.0 2.0 0.37 2 1024 2.3: 1.0: 1.23 80 10.7 10.7 4.3 <1.0 3 2: 1: 0.94 4th 2: 1: 1.00 5

(1) Diisocyanate: polyester: chain extender ratio

(2) Relative viscosity determined at 30 ° C using a 1.0% solution of dimethylacetamide.

(3) Based on approximately 0.076 cm interlayers

(4) Based on the conventionally plasticized one described above Polyvinyl butyral glass laminate standard.

The data in Table I above clearly shows the superiority of polyurethane interlayers and glass laminates made therefrom of the present invention.

Examples 1 and 2 show that a change in the ratio of reactants is a change the mean fracture height leads. Therefore one can do a lot

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flatter mean fracture height curve can be obtained when the mean fracture height is plotted against the temperature is made by a knowledgeable selection of the ratio of the reactants. That means that one Safer windshield can be created over a wide temperature range, which is a significant and important contribution to glass laminate production represents and for the safety of motorists. Examples 3 and 4 further show that the middle The height of the break can be regulated by a knowledgeable selection of the reactants and their proportions. In Example 3, the amount of diisocyanate and chain extender is greater than that used in Example 4 Amount increased. The result of the mean fracture height tests for Example 3 shows a reduction in the -18 ° C mean break heights and a corresponding increase in the 49 ° C mean break heights compared to Example 4. This gives a flatter impact strength curve over a wide temperature range compared to Example 4.

Note that all are in accordance with the present

Laminates made in accordance with the invention have a very low haze value. This sign of clarity and ease of light transmission clearly shows the suitability of these materials for use in glass bodies, particularly windshields, which are used in vehicles.

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EXAMPLES 6 TO 9 (COMPARATIVE EXAMPLES) The following examples serve to show the unacceptable level of haze obtained when a mixture of two different isomeric mixtures of 4,4'-methylenebis (cyclohexyl isocyanate) is used, one component of the mixture being one Has isomer content outside the range given above. The general one-step procedures of Examples 3 and 4 are used herein to prepare the polymer using poly (1,4-butylene adipate) (FP = 49-5O ° C) and 1,3-propanediol as chain extenders. The 4,4'-methylenebis (cyclohexyl isocyanate) used is a mixture of (1) a commercially available mixture -Hylene W (supplier: duPont) and (2) a commercially available mixture -Nacconate H-12 (supplier: Allied Chemical) . The Hylene W used in Example 6 has a trans-trans content of about 21% by weight, a cis-cis content of about 15% by weight and a cis-trans content of about 64% by weight. The Hylene W used in Examples 7 and 8 has a trans-trans content of about 20% by weight, a cis-cis content of about 17% by weight and a cis-trans content of about 62% by weight. -%. The Nacconate H-12 has a trans-trans content of about 49% by weight, a cis-cis content of about 9% by weight and a cis-trans content of about 42% by weight.

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In Examples 6 to 8, the poly (1,4-butylene adipate) used a molecular weight of 1007, while, in Example 9, its molecular weight is 1024. In each example is the ratio of isocyanate: poly (1,4-butylene adipate): 1,3-propanediol equal to 2: 1: 0.94. The curing conditions for the polymers in Examples 6 to 9 are 96 hours at 90.degree.

Table II

Summary of Comparative Examples 6-9 trans-
trans- cis-
cis- cis-
trans- relative
Cloudiness Isomer
(*) Iso-
meres Isome
res (2) At-
QV% 4 Λ 1 Used
relationship 23.5
27.6
34.8
49.2 14.5
15.2
13th
8.8 62
57/2
52.2
42 15.25
5.60
16.05
cloudy Hylene Nacco-
W nate H-12 6th
7th
8th
9 9 1
7.5 2.5
5 5
O 10

(1) Relative viscosity, determined at 30 ^° C. using a 1.0% strength solution of dimethylacetamide

(2) Based on the conventionally plasticized polyvinyl butyral glass laminate standard described above.

A comparison of Examples 6 through 9 with Examples 1 through 5 clearly shows the superior clarity that is obtained when a 4,4'-methylenebis (cyclohexyl isocyanate) having an isomer content within the specified range is used. Note that the Haze height of the laminates of Examples 6 to 8, where

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a mixture of two different isomer mixtures is used is much larger than that obtained in Examples 1-5. Also note that Example 9, the commercially available mixture of isomers that are outside of the specified ranges also used shows undesirable haze. The ones in the examples The haze level obtained 6 to 9 makes these laminates suitable for use as vehicle windshields unacceptable where high-grade optical qualities are required.

Examples 10-21

Examples 10-21 serve to illustrate some changes in the reactants and the ratio of the To show reaction partners that are possible within the scope of the present invention.

Examples 10 and 18-21 are prepared using the I-stage procedure described above, while Examples 11-17 are made using the 2-step process. The examples 14-16 are made using an acetic acid catalyst while the others are dibutyltin diacetate use as a catalyst. In each example the diisocyanate used is 4,4'-methylenebis (cyclohexyl diisocyanate) that used in Examples 1-5.

The poly (ethylene-

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adipat) has a melting point of 49 - 50 ° C, while that used in Example 17 has a melting point of 53-55 ° C. That used in Examples 18-21 Poly (1,4-butylene adipate) (PBA) has a melting point from 49 - 50 ° C. A summary of these examples is given in Table III below.

Table III

Summary of the examples 1O26 Polymer together
! setting NCO: GIy-
kol: KV
(D 10 - Time
Hours. 21 rela
tive
Tru
exercise
(3) 1019 Chain
extend
gerer (5) 2: 1: 0.94 96 clear at
game Polyester-H)
Compo- Molecular
nent 1 ar w. η 1,2-XD 2: 1: 0.95 Reaction
condition
gene 96 n _r (2) 0.62 P £ A η 1,3-PD 2: 1: 0.95 Temp.
⁰ C 96 1.89 0.62 Il η 1,4-BD 2: 1: 0.95 90 96 3.83 0.36 IO II Il 1,3-PD 2: 1: 0.95 80 96
48 3.42 clear 11 ti η 1,3-PD 2: 1: 0.95 80 96
48 3.41 clear 12th 71 2Ö17 1,3-PD 2: l: O _r 95 80 96
48 2.44 clear 13th Il ! ΟΙΟ 1,3-PD 2: 1: 0.95 80
1OO 96 2.70 clear 14th Ii 1010 1,3-PD 3: 1: 1.9O 80
1OO 96 1.62 0.48 15th 3! 1007 1,3-PD 3: 1: 1.95 80
100 96 2.79 clear 16 ΡΒΆ 1010 _t _ 1,3-PD 3: 1: 1.91 80 96 2.24 clear 17th Il 1,3-PD 3: 1: 1.91 80 96 1.57 clear 18th Il (1,3-PD
(1,4-BD 90 19th SI 90 1.62 20th 90 21

(1) Ratio of diisocyanate! Polyester: chain extender

(2) Relative viscosity determined at 30 ° C using a 1.0% solution of dimethylacetate

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amide

(3) Relating to the conventionally plasticized one above described polyvinyl butyral glass laminate standard

(4) PÄA - polyethylene adipate

PBA - Poly (1,4-butylene adipate)

(5) 1,2-AD - 1,2-ethanediol 1,3-PD - 1,3-propanediol 1,4-BD - 1,4-butanediol

* 1/1 ratio

Examples 10-17 show the use of polyethylene adipate as polyester with Example 17 using a high molecular weight material. Example 10 uses 1,2-Äthandioi as a chain extender, while Example 21 used a 1: 1 mixture of 1,3-propanediol and 1,4-butanediol. Examples 18-21 show a higher ratio of diisocyanate in the polymer composition. Notice the extraordinary clarity in all of the above compositions.

Examples 22-36 (Comparative Examples) These examples demonstrate the use of other well-known diisocyanates in making the previous polyurethane materials. Polyethylene adipate (Examples 35 and 36) and poly (1,4-butylene adipate) (Examples 22-34) are used as the polyester reactants and 1,3-propanediol and 1,4-butanediol

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as a chain extender. The polyurethane is produced according to the methods given above. The examples 23 and 27 are produced via a 1-step process, while in the other examples the 2-step process is used. In each example, the polyurethane obtained is not for use as an interlayer material acceptable in vehicle windshields because of their poor optical properties. This in polyethylene adipate used in Examples 35 and 36 and that used in Examples 22, 23, 29, 30 and 31 Poly (1,4-butylene adipate) has a melting point from 49 - 50 ° C. The poly (1,4-butylene adipate) used in Examples 24 to 28 and 33 to 34 has one Melting point of 54 - 56 ° C. The results of these examples are summarized in Table IV below.

Table IV

Summary of Comparative Examples 22-36 Isocya
nat Chains
extend NCO poly
ester: KV Reaction Time
Hours. η Rela (4) gerer
(5) (D condition
gene 24 tive
_r (2) Trü at XDI BD 2: 1: 0.95 Temp.
⁰ C 24 2 exercise game Polymer composition Il Il 2: 1: 1.00 90 24 1 , 50 11.65 Poly-
ester MDI Il 2: 1: 0.95 90 24 , 39 cloudy 22nd molecular
largew. Il Il 3: 1: 1.95 90 24 - opaque 23 1011 Il Il 4: 1: 2.95 90 24 _ Il 24 -Il Il Il 2: 1: 0.95 90 24 _ Ii 25th 1956 Il Il 2: 1: 0.95 90 24 _ ι · 26th Il HMD Il 2: 1: 0.95 80 48 _ n 27 Il Il PD 3: 1: 1.95 80 cloudy 28 Il 100 _ Il 29 2000 30th 1011 1020

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- 23 Continuation of the table

31 lOlO HMD PD 3: 1: 1.85 80 72 32 2000 Il Il 2: 1: 0.95 90 24 33 Il ti BD 2: 1: 0.95 90 24 34 Il ti PD 2: 1: _O, 95 100 24 35 1023 η Il 2: 1: 0.95 90 24 36 Il π BD 2: 1: 0.95 90 24

(1) Diisocyanate: polyester: chain extender ratio.

(2) Relative viscosity, determined at 30 ^° C. using a 1% strength solution of dimethylacetamide.

(3) Based on the conventionally plasticized polyvinyl butyral glass laminate standard described above.

(4) XDI - xylene diisocyanate

MDI - 4,4 ^I -ethylene bis (phenyl isocyanate) HMD - hexamethylene diisocyanate

(5) BD - 1,4-butanediol PD - 1,3-propanediol

The data of the above Table IV show the low optical properties which are obtained in polyurethane interlayers, if other diisocyanates are used as the isomeric mixture of 4.4 ^{f-methylenebis} (cyclohexyl isocyanate) of the present invention. Aromatic diisocyanates, such as those used in Examples 22-28, result in polyurethanes which, by virtue of their exceptionally low optical properties

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Properties are marked. Those in Examples 29 to 36 using hexamethylene diisocyanate The polyurethanes produced also exhibit a degree of haze that makes them suitable for use as an intermediate layer in laminates makes it unsuitable for use in vehicles. The data in Table IV is from further interest in view of the fact that 4,4'-methylenebis (phenyl isocyanate) has a structure which is quite analogous to 4,4'-methylenebis (cyclohexyl isocyanate) of the present invention. Despite the fairly similar chemical structure, that fails Phenyl isocyanate, however, in the process of producing polyurethanes with uniform properties, which in the after the tubes, materials obtained from the present invention being found.

Examples 37-38 (Comparative Examples) Examples 37 and 38 demonstrate the use of polyoxytetramethylene glycol in place of the specific polyester component used in the present invention. In each example, the 1-step process described above is used to produce the polyurethane. The glycols with molecular weights of 670 and 1030 are used in Examples and 38, respectively. In each example the diisocyanate used is the mixture of isomers used in Examples 1-5 and the 1,3-propanediol is used as a chain

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extended used. The test results of this Bei games are listed in Table V below.

Table V

Summary of Comparative Examples 37 and 38

_B * uw ^ jniea. Reaction together conditions

Time

NCOiGlycol: oC hrs.

37 —M
3: 1: 1 , 9O 80 144 1 , 39 cloudy 38 3: 1: 2 , 0 8O 96 2 , 08 4.00

Note that replacing the polyoxytetramethylene glycol for the preferred polyesters with a polyurethane which results in an unacceptable level of haze in the laminate. Other examples were made using made of polyoxytetramethylene glycol with a molecular weight of 670, the ratio of Diisocyanate: glycol: chain extender equals 2: 1: 0.95 amounts to. These materials show much better clarity than those made in Examples 37 and 38. However, the tear impact energies of these materials are in the range of 337 up to 380 kg-cm / cm. Experience has shown that polyurethane interlayer materials with such a low level of tear energies in glass laminates result in a low level of impact strength.

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3Q9830 / 1105

Examples 39 to 51

The following Examples 39 through 51 below demonstrate the superior impact strength obtained with the interlayer materials of the present invention. Also for comparison purposes, interlayer materials made from other diisocyanates are used as the preferred isomer mixture of 4,4'-methylene-bis (cyclohexyl isocyanate). The polyurethane materials are made according to the procedures outlined above. Examples 41, 42 and 51 used the 1-step process while the other examples were prepared using the 2-step process. Examples 30 to 42 are prepared using the isomer mixture of 4,4 ^I- methylenebis (cyclohexyl isocyanate) used in Examples 1-5.

Examples 43 to 49 are prepared using hexamethylene diisocyanate. The examples and 51 use 4,4'-methylenebis (phenyl isocyanate). All The polyesters used have melting points in the range from 48 to 55 ° C.

A summary of these examples is given in Table VI below.

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30 9830/1105

Table VI Summary of Examples 39 through 51

CD
CO
OO
CO
O

example

Polymer composition

Polyester molecular chains or Glycol largew. longer (4) shorter

(5)

NCO: glycol: KV (1)

Reaction conditions temp. Time

⁰ C h

Average breaking height of the laminate (meters) (3)

-18 ° C

39
40
41
42

PBA

Il

PAE

"
same

"

"

ro 50 Il Il 00 51 N Il

21 ° C

1020 BD η Il 2017 PD Il η

1927

45 Il PBA 1020 46 Il < ^C 4 °> x 670 47 Il Il η 48 Il fl Il

1030
2000

BD

PD

BD

2: 1: 1.00
2: 1: 0.95
3: 1: 1.91
3: 1: 1.91
2: 1: 0.95

2: 1: 0.95

2: 1: 0.95

2: 1: 0.95
2: 1: 0.95
2: 1: 0.95

2: 1: 0.95

3: 1: 1.95
3: 1: 1.95

96 72 96 96

22 2

84

48 96 48

22 2

24 24

1.82
3.15
2.66
3.38

4.0
3.4
8.1
7.3
6.1

2.84
8% gel

1.81
2.77

1.77

% Gel

6.7

2.25

7.0 9.3 5.9 6.4 3.0

2.4

3.4

2.4 2.4 3.0

4.0 4.6

49 ° C

4.0 3.4 2.7 2.7 2.4

2.4

ίΐ) Ratio of diisocyanate polyester: chain-reducing agent.

C2) Relative viscosity / determined at 30 ° C using a 1.0% solution of dimethylacetamide.

(3) Based on approximately 0.076 cm interlayers.

(4) paa - poly (ethylene adipate)
PBA - Poly (1,4-butylene adipate)

(C ₄ O) - polyoxytetramethylene glycol Ϊ5) BD -. 1,4-butanediol
PD - 1,3-propanediol

Note in Table VI above that the laminates made according to the teachings of the present invention (Examples 39 to 42) show better impact strength when determined by the mean breaking height than the laminates obtained as polyurethane interlayers of the previous type (Examples 43 to 51).

Also note that the laminates made according to the present invention have an average breaking height, which would give a flatter curve if the mean fracture height was plotted against the temperature is, as such laminates, which are produced according to the previous type. In some cases, especially in Examples 44 and 46-51, is the mean break height at 21 ° C with poor optical clarity of laminates connected using the

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309830/1105

Polyurethane interlayers of the previous type have been made and do not warrant further testing.

Example 52

This example is given to demonstrate the printability of the polyurethane interlayers of this invention to obtain a colored gradient in the obtained laminate.

The interlayer material produced in Example 1 is coated with an ink containing anthraquinone dyes in dissolved in a solvent containing N, N-dimethylformamide. The plate is dried and subsequently laminated between glass plates in the conventional manner. The laminate obtained is thereby characterized by having a blue colored gradient similar to that of conventional windshields is preserved.

Abbreviated edge stability tests were performed to test the laminate's ability to delaminate to withstand high humidity conditions. This is an index for long-term stability of the laminate and is useful in predicting whether a given material is suitable for use as a windshield suitable for vehicles or not. The test laminates used are from those in the examples 3, 4 and £ 5 intermediate layers described above manufactured. A commercially available polyurethane

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309830/1105

"Texin 480" material (a product of Mobay Chemical Company) is also included. This latter polyurethane material is based on 4,4 · methylenebis (phenyl isocyanate). The results of the edge stability test are given in Table VII below.

Table VII

Edge stability test results test example Two (2) Week Test Four (4) weeks goes goes 3 goes - 4th goes _ 45 fails Texin 480 fails

Note in Table VII above that the interlayers of Examples 3 and 4 made in accordance with the present invention show excellent edge stability even after a 4 week test period. On the other hand, the one prepared according to Example 45 using hexamethylene diisocyanate fails Intermediate shift after a 2-week test period. The commercially available material based on 4.4 - Methylenebis (phenyl isocyanate) based also fails after a 2-week test period. These results that put together with other test results listed above, show the clear superiority of the interlayers of the present invention over the previous.

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309830/1105

The edge stability of the polyurethane interlayers of the present invention can be improved, by the glass and / or interlayer material with any of the common silane adhesion promoters is treated. These materials, also known as adhesives or fasteners, are if'-glycidyloxypropyl-trimethoxysilane, N-trimethoxysilylpropylethylenediamine etc..

If necessary, the surface of the intermediate layer and / or the glass can be treated with an epoxy resin. Optionally, the silane and / or the epoxy resin can be mixed with the polyurethane interlayer material Mix. When choosing the type and quantity of materials, it must be ensured that there is no color in the intermediate layer is introduced. As stated above, the interlayers are polyethylene of the present invention can also be used as an intermediate layer component in laminated glass bodies, transparent synthetic resin plates are used in place of the glass plate. Examples of such transparent sheets are polystyrene, polyvinyl chloride, polycarbonate, polymethyl methacrylate, poly (acrylonitril styrene), Poly (acrylonitrile-butadiene-styrene) etc. Also to be considered are multilayer laminates, such as a glass / polyurethane interlayer / polycarbonate sheet / Polyurethane interlayer / glass laminate and a glass / polyurethane interlayer / clear synthetic resin

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309830/1105

panel laminate.

The present invention also contemplates the use of additives and additives commonly found in interlayer material be used for glass laminates. These are antioxidants, thermal ones Stabilizers, ultraviolet stabilizers, dyes, pigments, plasticizers and additives for controlling the amount of adhesion of the intermediate layer to the glass.

309830/1105

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Claims (3)

Claims pi. Polyurethane intermediate layer for laminated glass bodies, characterized in that it consists essentially of the polymerisation reaction product of 1) a diisocyanate which is an isomeric mixture of 4,4'-methylenebis (cyclohexyl isocyanate), 2) a hydroxyl terminated polyester with a melting point above 42 ° C and a Molecular weight of 500-4000, which is the condensation product of a dicarboxylic acid and a diol compound is and 3) a chain extender that is an aliphatic or is an alicyclic diol with 2-16 carbon atoms, the mixture of hisocyanate isomers has a transtrans content from 0-30% by weight, a cis-cis content of 0-25% by weight and a cis-trans content of 45-90% by weight and that the ratio of Diisocyanate / polyester / chain extender in the polyurethane intermediate layer in the range of 1.5 / 1.0 / 0.5 up to 4 / 1.0 / 3.0. 2. Interlayer according to claim 1, characterized in that the polyester is the condensation product a straight chain aliphatic acid with 2-10 - 34 - 3 0 9 8 3 0/1105 Carbon atoms and a straight-chain oC-, tU-aliphatic Diol with 2-10 carbon atoms is that the polyester has a molecular weight of 800-1200 that the Chain extender 1,3-propanediol or 1,5-pentanediol and that the ratio of diisocyanate / polyester / chain extender in the polyurethane intermediate layer ranges from 2.0 / 1.0 / 0.94 to 2.3 / 1.0 / 1.23. 3. Laminated glass body with a polyurethane intermediate layer according to claim 1. 309830/1105